Supporting Information

Application of Bodipy-C70 Dyad in Triplet-Triplet

Annihilation Upconversion of Perylene as a Photosensitizer

Yaxiong Wei, Min Zheng, Qiaohui Zhou, Xiaoguo Zhou,* Shilin Liu

Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative

Innovation Center of Chemistry for Energy Materials), Department of Chemical Physics,

University of Science and Technology of China, Hefei, Anhui 230026, China

*Author to whom correspondence should be addressed.

Electronic mail: xzhou@ustc.edu.cn

Contents

1. 1H NMR and HR TOF-MS spectra

2. Dynamic decay curves of intermediates

3. TTA upconversion spectra

4. Absorption and fluorescence spectra of perylene in toluene

5. Detailed theoretical calculations of Bodipy-C70 and C70

6. Optimized molecular geometries of Bodipy-C70 at the ground and lowest triplet

states.

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018

1. NMR and HR-MS spectra

Figure S1. 1H NMR spectrum of Bodipy-C70 in CDCl3 (400 MHz).

Figure S2. High-resolution TOF MS with MALDI of Bodipy-C70.

2. Dynamic decay curves of intermediates

Figure S3. The decay curves at 671 nm of the Bodipy-C70/perylene system. c[Bodipy-C70] =1.0×10-5 M, c[Perylene]=0, 16, 32, 80 ×10-5 M, in deaerated toluene, 25°C, with a pulsed laser excitation at 532 nm, 10 ns, 8 mJ/pulse.

Figure S4. The decay curves at 709 nm of the C70/perylene system. c[C70] =1.0×10-5 M, c[Perylene]=0, 4, 12, 24 ×10-5 M, in deaerated toluene, 25°C, with a pulsed laser excitation at 532 nm, 10 ns, 8 mJ/pulse.

Table S1. The apparent lifetimes (τ) of Bodipy-3C70* and 3C70

* at different concentration of perylene, by fitting the decay curve of absorption at 671 nm or 709 nm

　 Perylene / 10-4M τ0 τ τ(0)/τ(c)‒1 TTET efficiency0 80.1 23.02 0 0

0.8 80.1 11.9 0.93 0.4831.6 80.1 10.6 1.17 0.5402.4 80.1 7.2 2.20 0.6873.2 80.1 6.9 2.34 0.7004 80.1 6.38 2.61 0.7238 80.1 3.2 6.19 0.861

16 80.1 1.63 13.12 0.92924 80.1 1.11 19.74 0.95232 80.1 0.77 28.90 0.967

Bodipy-C70

48 80.1 0.48 46.96 0.9790 75.53 18.86 0 0

0.4 75.53 5.11 2.69 0.7290.8 75.53 3.29 4.73 0.8261.2 75.53 2.02 8.34 0.8931.6 75.53 1.54 11.25 0.918

C70

2.4 75.53 1.02 17.49 0.946

3. TTA upconversion Spectra

Figure S5. Dependence of the upconverted fluorescence of the system of C70 and perylene on the excitation power density, c[C70] =1×10-5 M, c[Perylene]= 3.2×10-3 M, in deaerated toluene, 25°C, with photoexcitation at 532 nm.

Figure S6. Dependence of the steady-state fluorescence of Bodipy on the excitation power density, c[bodipy] =1×10-5 M, in toluene, 25°C at 532 nm excitation.

Figure S7. The upconverted fluorescence intensity of Bodipy-C70 and perylene vs. laser exposure time (532 nm, 4000 mW/cm2), c[Bodipy-C70]=1×10-5 M, c[Perylene]= 3.2×10-3 M; in deaerated toluene, 25°C.

Figure S8. The upconverted fluorescence intensity of C70 and perylene vs. laser exposure time (532 nm, 4000 mW/cm2), c[C70]=1×10-5 M, c[Perylene]= 3.2×10-3 M; in deaerated toluene, 25°C.

Figure S9. Dependence of the upconverted fluorescence in the system of Bodipy-C70

and perylene on the concentration of perylene, c[Bodipy-C70] =1×10-5 M, 532 nm, 2000 mW/cm2. in deaerated toluene, 25°C.

Figure S10. Dependence of the upconverted fluorescence in the system of C70 and perylene on the concentration of perylene, c[C70] =1×10-5 M, 532 nm, 2000 mW/cm2. in deaerated toluene, 25°C.

4. Absorption and fluorescence spectra of perylene in toluene.

Figure S11. Normalized UV-Vis absorption and fluorescence emission spectra of perylene in toluene.

5. Detailed theoretical calculations of Bodipy-C70 and C70

5.1 The calculation results of singlet-singlet transition absorption.Table S2. Absorption wavelengths (λ), oscillator strengths (f), main electronic configurations and characters of the singlet-singlet transitions of C70 monomer and Bodipy-C70 dyad, calculated at TD-DFT//B3LYP/6-31G(d) level. a

C70 Bodipy-C70

wavelength / nm f wavelength / nm f configuration b character

575.15 0.0032 613.58 0.0172 329→331 C70→C70

575.11 0.0032 588.51 0.0029 329→333 C70→C70

531.72 0.0704 574.88 0.0040 330→331 Bodipy→C70

531.63 0.0703 552.09 0.0022 330→332 Bodipy→C70

499.52 0.0057 541.17 0.0019 328→333 C70→C70

457.07 0.1255 535.7 0.0198 330→333 Bodipy→C70

457.05 0.1256 531.88 0.0680 328→332 C70→C70

436.94 0.0445 525.04 0.0346 327→333 C70→C70

406.81 0.0064 523.78 0.0683 327→332 C70→C70

370.11 0.4130 509.26 0.0015 329→335 C70→C70

354.11 0.0041 503.65 0.0053 326→331 C70→C70

354.06 0.0041 477.02 0.0028 325→332 C70→C70

332.38 0.0831 476.86 0.0029 324→331 C70→C70

329.55 0.2425 472.65 0.0112 322→331 C70→C70

329.54 0.2422 468.23 0.0035 324→332 C70→C70

466.83 0.0048 321→331 C70→C70

465.61 0.0307 324→331 C70→C70

464.36 0.0173 325→331 C70→C70

461.22 0.0043 328→335 C70→C70

460.1 0.0103 322→332 C70→C70

456.52 0.0064 321→332 C70→C70

451.76 0.6449 330→334 Bodipy→Bodipy

450.4 0.0941 330→335 Bodipy→C70

448.88 0.0486 327→335 C70→C70

441.43 0.0245 329→334 C70→Bodipy

440.73 0.0596 329→334 C70→Bodipy

439.64 0.0343 324→333 C70→C70

437.77 0.0243 321→333 C70→C70

433.94 0.0508 322→333 C70→C70

432.71 0.0202 323→331 Bodipy→C70

428.88 0.0087 329→336 C70→C70

422.94 0.0019 319→332 C70→C70

421.6 0.0011 326→335 C70→C70

418.58 0.0304 320→331 C70→C70

413.43 0.0040 323→332 Bodipy→C70

412.45 0.0058 328→334 C70→Bodipy

412.43 0.0078 328→334 C70→Bodipy

408.79 0.0337 328→336 C70→C70

404.43 0.0049 319→333 C70→C70

402.95 0.0015 327→334 C70→Bodipy

401.62 0.0014 320→332 C70→C70

396.98 0.0032 330→336 Bodipy→C70

393.39 0.0031 320→333 C70→C70

386.2 0.0028 325→335 C70→C70

384.75 0.1333 324→335 C70→C70

384.33 0.0679 324→335 C70→C70

382.25 0.2131 323→334 Bodipy→Bodipy

381.75 0.0038 321→335 Bodipy→C70

378.76 0.0262 322→335 C70→C70

377.2 0.0334 321→335 Bodipy→C70

374.74 0.0017 326→334 C70→Bodipy

368.45 0.0025 330→337 Bodipy→C70

364.56 0.0158 327→337 C70→C70

359.59 0.0063 318→331 Bodipy→C70

355.93 0.0019 325→334 C70→Bodipy

354.51 0.0064 317→331 Bodipy→C70

353.41 0.0037 319→335 C70→C70

353.01 0.0019 324→334 C70→Bodipy

352.66 0.0050 318→332 Bodipy→C70

351.72 0.0079 325→336 C70→C70

351.56 0.0142 318→332 Bodipy→C70

350.76 0.0372 318→334 Bodipy→Bodipy

349.15 0.0014 321→334 C70→Bodipy

347.51 0.0297 327→338 C70→C70

346.85 0.0125 327→338 C70→C70

345.08 0.0024 320→335 C70→C70

344.91 0.0020 318→333 Bodipy→C70

340.88 0.0029 320→334 Bodipy→Bodipy

339.58 0.0067 326→337 C70→C70

338.83 0.0026 317→332 Bodipy→C70

337.1 0.0407 317→333 Bodipy→C70

335.86 0.0072 326→337 C70→C70

334 0.043 317→333 Bodipy→C70

332.79 0.0238 326→338 C70→C70

332.32 0.0085 316→331 Bodipy→C70

331.93 0.0408 322→336 C70→C70

330.55 0.0120 316→334 Bodipy→Bodipy

330.29 0.0365 325→337 C70→C70

330.18 0.0021 312→337 C70→C70

327.89 0.0016 312→337 C70→C70

326.71 0.0048 311→331 C70→C70

325.71 0.0025 312→332 C70→C70

324.98 0.0033 311→332 C70→C70

324.07 0.0041 316→332 Bodipy→C70

　 　 321.81 0.0124 329→339 C70→C70

a. Only the low-lying excited states with the oscillator strength f > 0.001 were listed. b. The main electronic configurations are shown.

Figure S12. The frontier orbitals involved in the singlet-singlet transitions of Bodipy-C70. Toluene was used as the solvent in the calculations.

Figure S13. The singlet-singlet absorption spectra of C70 monomer (a) and the C70 unit in Bodipy-C70 (b). Toluene was used as the solvent in the calculations.

The singlet-singlet transitions were noted as the sticks in Figure S13, and the

absorption spectra were simulated by taking into account the temperature distributions

and instrument resolution with a Gaussian lineshape of the ca. 20 nm width. It should

be demonstrated that only the transitions of the C70 unit in Bodipy-C70 dyad were

shown in Figure S13(b).

For the C70 monomer, the peaks at 456 nm, 369 nm and 331 nm looked sharper,

which were slightly shifted and moderately broadened in absorption spectrum of

Bodipy-C70. These differences were normal because the derivatization of C70 unit

destroyed its original symmetric molecular structure, and caused degeneration of

electronic transitions. As shown in Figure 13, the theoretical calculations confirmed

the changes as the more sticks were observed in the dyad.

5.2 The calculation results of triplet-triplet transition absorption.

Table S3. Transition wavelengths (λ), oscillator strengths (f), main electronic configurations and characters of the triplet-triplet transition of C70 monomer and Bodipy-C70 dyad, calculated at TDDFT//B3LYP/6-31G(d) level. a

C70 Bodipy-C70

wavelength / nm f wavelength / nm f composition characterb

648.5 0.0106 656.11 0.0041 331A→337A Bodipy-Bodipy

591.15 0.0013 639.03 0.1006 317B→330B Bodipy→Bodipy576.46 0.0010 638.7 0.0008 328B→331B C70→C70

563.45 0.0127 631.44 0.0491 324B→330B C70→Bodipy547.2 0.0047 613.27 0.0010 321B→330B C70→Bodipy

542.77 0.0012 613.08 0.0157 329B→331B C70→C70

540.35 0.0010 587.92 0.0030 329B→333B C70→C70

536.05 0.0086 576.61 0.0269 316B→330B Bodipy→Bodipy522.88 0.0096 565.53 0.0010 328B→331B C70→C70

520.15 0.0327 539.72 0.0013 329A→334A C70→C70

515.43 0.0163 532.57 0.0725 329A→333A C70→C70

510.83 0.0330 524.94 0.0317 328A→334A C70→C70

500.25 0.0112 523.68 0.0668 328A→333A C70→C70

486.32 0.0039 509.2 0.0014 330A→335A C70→C70

485.38 0.0038 503.61 0.0040 326B→331B C70→C70

475.76 0.0041 476.93 0.0021 325A→333A C70→C70

472.85 0.0015 476.83 0.0026 324A→332A C70→C70

472.17 0.0020 472.65 0.0072 323A→332A C70→C70

467.26 0.0148 468.25 0.0021 324A→333A C70→C70

461.24 0.0246 466.97 0.0049 322A→332A C70→C70

460.65 0.0032 465.38 0.0221 324B→331B C70→C70

458.58 0.0335 464.22 0.0158 325A→332A C70→C70

452.27 0.0018 460.99 0.0042 328B→334B C70→C70

447.64 0.0796 460.05 0.0070 323A→333A C70→C70

443.01 0.0074 456.54 0.0060 322A→333A C70→C70

437 0.0012 454.75 0.0096 331A→340A Bodipy→C70

434.08 0.0031 448.88 0.0349 327B→334B C70→C70

429.11 0.0130 444.79 0.0035 326A→332A Bodipy→C70

424.2 0.0044 440.58 0.0347 325A→334A C70→C70

413.37 0.0217 438.51 0.0534 324A→334A C70→C70

413.1 0.0075 438.36 0.0013 331A→340A Bodipy→C70

410.8 0.0014 437.28 0.0167 321B→330B C70→Bodipy407.01 0.0027 435.07 0.0050 331A→348A Bodipy→Bodipy404.14 0.0111 434.07 0.0596 332A→334A C70→C70

395.96 0.0024 428.87 0.0076 330A→336A C70→C70

　 428.17 0.0025 326A→333A Bodipy→C70

　 424.96 0.0012 313B→330B C70→Bodipy

　 423.04 0.0162 321A→332A Bodipy→C70

　 421.97 0.0062 320B→331B C70→C70

　 421.51 0.0037 326B→334B C70→C70

a. Only the low-lying excited states with the oscillator strength f > 0.001 were listed. b. The major configurations are shown.

Figure S14. The frontier orbitals involved in the triplet-triplet transition excited states of Bodipy-C70. Toluene was used as a solvent in the calculations.

Figure S15. The triplet-triplet transition absorption states of C70 monomer (a) and the C70 unit in Bodipy-C70 dyad (b). Toluene was used as a solvent in the calculations.

The triplet absorption bands were calculated by TD-DFT as mentioned above.

The C70 monomer had four absorption bands in the visible region at 648 nm, 563 nm,

514 nm and 453 nm, respectively. The four triplet bands were also found for the C70

unit of Bodipy-C70, at 629 nm, 577 nm, 528 nm and 440 nm, although there were

some wavelength shifts. Similar to the singlet-singlet transition in Figure S13,

derivatization of C70 unit in the dyad also caused degeneration of electronic transitions.

The main triplet-triplet absorption bands including were summarized in Table S4.

Table S4. Transition energies (eV), wavelength (λ), oscillator strengths (f), major electronic configurations and CI coefficients of the triplet-triplet absorption transition of Bodipy-C70 and C70, calculated at TDDFT//B3LYP/6-31G(d) level. a

compoundelectronic

transitionexcitation energy fb composition c CI characterd

T1→T3 0.4907eV / 2526.68nm 0.0036 211A→212A 0.77659 C60

209B→210B 0.62659 C60

T1→T14 1.2697eV / 976.5nm 0.0335 211A→215A 0.78814 C60

202B→210B 0.58938 C60

T1→T18 1.9119eV / 648.5nm 0.0107 200B→210B 0.94073 C60

C70

T1→T25 2.2004eV / 563.45nm 0.0127 210A→213A 0.57787 C60

208B→211B 0.5432 C60

T1→T30 2.2658eV / 547.2nm 0.0046 208A→212A 0.62663 C60

T1→T20.6873 eV / 1803.95

nm0.0003 331A→332A 0.97747

C60

T1→T51.2320 eV / 1006.39

nm0.0122 325B→330B 0.75179

Bodipy

329B→330B 0.44522 Bodipy

T1→T18 1.9402 eV / 639.03 nm 0.1005 317B→330B 0.61554 C60

324B→330B 0.34347 C60

T1→T20 1.9635 eV / 631.44 nm 0.0491 317B→330B 0.46767 Bodipy

324B→330B 0.63115 Bodipy

T1→T28 2.0223 eV / 613.08 nm 0.0157 330B→332B 0.64379 Bodipy

Bodipy-C70

329B→331B 0.64553 Bodipy

a. Only the triplet-triplet absorption transition with the larger oscillator strength were listed. b. No spin-orbital coupling was considered. c. The major configurations are shown.d. Triplet-triplet absorption transition locates in the unit of bodipy-C70.

In the present experiment, there was a very strong ground-state bleaching band in

transient absorption spectrum of C70 monomer, which markedly covered the nearby

bands like 438 nm and 543 nm. However, no ground-state bleaching existed for the

bodipy-C70 dyad. Thus, only the transitions above 700 nm and below 410 nm could be

clearly compared. Their blue-shifts were clearly found from the C70 monomer to the

dyad, which were consistent with the above theoretical conclusions. In the other

words, the positive absorption peaks observed for Bodipy-C70 dyad could be naturally

ascribed to the blue-shifts of the corresponding bands of the 3C70* unit.

6. Optimized Molecular Geometries of Bodipy-C70

a. Optimized S0 state geometry of Bodipy-C70.

C -1.83384400 2.99322900 -1.02051800 C -0.45674800 3.55466900 -1.30125800 C 1.24247000 5.05546400 -0.88463400 N -0.16541800 4.81074900 -0.61268800 C -1.01489400 5.92849800 -1.00947900 C -7.15728900 -4.76922100 -0.36788300 C -7.54545000 -3.53184700 0.14880200 C -8.00622600 -2.52101300 -0.70597200 C -8.07731200 -2.76836900 -2.08337600 C -7.69426900 -4.00866800 -2.59735000 C -7.23190800 -5.01052500 -1.74146400 C -8.42077600 -1.19462300 -0.15420200 C -9.72854800 -1.03385100 0.33148400 C -7.50158500 -0.12910500 -0.13265300 C -10.84210700 -1.93839100 0.40389500 C -11.88409600 -1.21644300 0.97474600 C -11.43160600 0.09123900 1.24149700 N -10.14402700 0.19711500 0.85613100 N -7.88343000 1.12066400 0.36821200 C -6.83372500 1.95954900 0.29268600 C -5.72255200 1.27610300 -0.27083800 C -6.13212600 -0.03911200 -0.53946300 C -10.94343600 -3.37160400 -0.02840500 C -5.25069900 -1.12049500 -1.09428100 C -12.19340400 1.22767100 1.84121300 C -6.92617100 3.38552100 0.73204400 B -9.28765300 1.49065900 0.92850700 F -9.17351400 1.92285400 2.25081800 F -9.87199100 2.49109000 0.14524800 C -4.39166500 1.86749900 -0.52584500 C -3.67210500 2.51670200 0.49391200 C -2.41646800 3.06976800 0.25225200 C -2.54951900 2.35916400 -2.04211400 C -3.80534600 1.80428100 -1.80089600 H -0.36447400 3.68751400 -2.39777800 H 1.63559300 5.84874800 -0.24142500 H 1.41045500 5.35800000 -1.93641500 H -2.05829700 5.70606300 -0.77368400 H -0.94072400 6.15437400 -2.08981800

H -0.71758400 6.82162600 -0.45085200 H -6.79783400 -5.54405400 0.30365100 H -7.48885900 -3.34438000 1.21761200 H -8.43534900 -1.98834800 -2.74971100 H -7.75620000 -4.19041200 -3.66681400 H -6.93141000 -5.97439600 -2.14271100 H -12.88079600 -1.58514700 1.18156000 H -11.96958600 -3.72532700 0.11096200 H -10.67678500 -3.50525000 -1.08187500 H -10.27995800 -4.02483400 0.54834800 H -5.30534300 -2.03566100 -0.49832500 H -5.52933000 -1.39604900 -2.11817800 H -4.21086500 -0.78478900 -1.11103000 H -12.23834400 2.07105300 1.14376600 H -13.21032500 0.91629200 2.09196500 H -11.69531700 1.59259200 2.74552000 H -6.04847900 3.94760000 0.40786400 H -7.82762000 3.84946300 0.32177800 H -7.00436800 3.45152500 1.82349400 H -4.09589600 2.57104600 1.49286100 H -1.87728300 3.56583000 1.05322900 H -2.12436900 2.30514100 -3.04178100 H -4.34987700 1.33530500 -2.61539800 C 4.37812100 3.66486600 -0.73031500 C 3.18064700 3.46073500 -1.49608600 C 4.00887900 3.75559100 0.66484600 C 1.94238600 3.69113000 -0.62631800 C 2.58354300 3.60430900 0.76233700 C 3.21286800 2.58989500 -2.56689200 C 4.44178500 1.92290900 -2.93113100 C 2.12804900 1.62202100 -2.78634700 C 4.13379100 0.58475800 -3.38319300 C 2.71667900 0.39918000 -3.29042700 C 0.75690800 2.62662300 -0.87367100 C 1.06246100 1.56377000 -1.92338300 C 0.46897500 1.71803400 0.32149000 C 0.56917500 0.28422600 -1.50519000 C 0.20703500 0.37830200 -0.12217200 C 2.05913900 2.87857400 1.80979600 C 0.97709700 1.91009100 1.58082100 C 2.92889500 2.30167200 2.80856500 C 1.20303400 0.77816200 2.45459100 C 2.39562900 1.01959100 3.20980500 C 4.86334700 3.23293300 1.64813300

C 4.30732400 2.48618200 2.73991200 C 6.09458300 2.57269500 1.26268900 C 5.19528000 1.38134100 3.04778800 C 6.30261800 1.43747700 2.13840600 C 5.58716700 3.05195600 -1.09452600 C 6.44828100 2.48452400 -0.07696400 C 5.61346300 2.15871600 -2.21708600 C 7.02224600 1.25742300 -0.59095500 C 6.50260400 1.05403500 -1.91194400 C 1.04209400 -0.93802400 -2.06350200 C 0.87271600 -2.10212000 -1.26996100 C 0.30415700 -0.75095500 0.74018900 C 0.50850200 -2.00918600 0.11582700 C 0.82240300 -0.54046400 2.08940100 C 1.51944700 -1.60197600 2.72594200 C 3.24229900 -0.04763300 3.62104000 C 2.71385500 -1.35840200 3.48190000 C 4.69859800 0.14016900 3.52911600 C 5.51533800 -0.99763900 3.28996300 C 6.94203300 0.25163400 1.68184500 C 6.62214100 -0.94271600 2.37952900 C 7.31653200 0.15783800 0.26205600 C 7.34189200 -1.12287900 -0.34985000 C 6.26631800 -0.25221600 -2.41829600 C 6.82382000 -1.32502600 -1.67216100 C 5.03770900 -0.49690300 -3.18969000 C 4.46712000 -1.79739800 -3.16889900 C 2.16277100 -0.87650700 -2.99907900 C 3.04834800 -1.98517100 -3.07411300 C 5.10846800 -2.89360800 -2.47008300 C 2.80546900 -3.19492800 -2.31495400 C 4.08208700 -3.77292300 -1.94894700 C 1.73518600 -3.25345300 -1.42975300 C 1.14237100 -3.10442100 0.81896900 C 1.89813200 -3.88864100 -0.13723900 C 1.64174000 -2.90259600 2.10053500 C 3.57971800 -2.51106900 3.32943300 C 2.91343400 -3.48016500 2.48358000 C 4.95354300 -2.33388600 3.23264300 C 6.74424400 -2.24518800 1.75138100 C 5.72215200 -3.11750900 2.28942900 C 7.09770900 -2.33373500 0.41173400 C 6.26296500 -2.66139200 -1.73406500 C 6.44342900 -3.29760100 -0.44709100

C 5.45285000 -4.14161000 0.06571300 C 4.24547800 -4.38222400 -0.70222600 C 3.12802200 -4.44117900 0.22369900 C 3.64776300 -4.23316500 1.56411600 C 5.08440400 -4.04994100 1.46480200

b. Optimized T1 state geometry of Bodipy-C70.

C 1.82816400 -2.98728600 -1.03145000 C 0.45141900 -3.54701000 -1.31765800 C -1.24833600 -5.04966700 -0.91056200 N 0.15971700 -4.80703600 -0.63685000 C 1.00867000 -5.92277300 -1.04069100 C 7.22399200 4.81181000 -0.40482000 C 7.59678400 3.57268000 0.11971600 C 8.03197300 2.53616500 -0.72139200 C 8.08526700 2.77512100 -2.10354300 C 7.71287900 4.01341600 -2.63086700 C 7.28102700 5.03501700 -1.78235100 C 8.43246200 1.21029200 -0.15927600 C 9.74646800 1.00455400 0.34349600 C 7.52086200 0.12054300 -0.12251000 C 10.89446900 1.91482700 0.42043800 C 11.92186700 1.18334400 0.99637300 C 11.46029400 -0.11650200 1.26538000 N 10.13939300 -0.20652100 0.86189900 N 7.89345600 -1.11030900 0.37298400 C 6.82036800 -1.96929600 0.29579000 C 5.71416800 -1.27775500 -0.26758100 C 6.12435800 0.03107700 -0.53539400 C 10.99080700 3.33984900 -0.02620100 C 5.26261600 1.13218600 -1.07288800 C 12.18526400 -1.26692100 1.86798300 C 6.93145800 -3.39155900 0.72041600 B 9.28292000 -1.49059300 0.94074800 F 9.16350000 -1.91962300 2.26758700 F 9.86549500 -2.50807400 0.17229500 C 4.38421100 -1.86694700 -0.52639100 C 3.66657700 -2.52697200 0.48772100 C 2.41040900 -3.07610000 0.24076900 C 2.54316600 -2.34272100 -2.04708400 C 3.79781300 -1.78815200 -1.80050000 H 0.36090000 -3.67319300 -2.41507400

H -1.64177100 -5.84637400 -0.27182900 H -1.41592200 -5.34640000 -1.96400600 H 2.05218200 -5.70297100 -0.80280500 H 0.93489100 -6.14135600 -2.12251300 H 0.71035700 -6.81934400 -0.48819900 H 6.88733100 5.60126400 0.26196600 H 7.54815500 3.39951100 1.19173300 H 8.42381300 1.98230400 -2.76560800 H 7.76184900 4.18018800 -3.70374800 H 6.99073200 5.99879500 -2.19183200 H 12.92192900 1.54167100 1.20546500 H 12.01409400 3.70111600 0.11621100 H 10.72957800 3.46047800 -1.08349000 H 10.31766200 3.99784300 0.53556900 H 5.31817800 2.03058600 -0.45007200 H 5.55808600 1.43835100 -2.08404900 H 4.21971100 0.80739400 -1.11271900 H 12.20236100 -2.11710700 1.17560800 H 13.21083100 -0.98598300 2.11934300 H 11.67323200 -1.61650200 2.77224000 H 6.03168700 -3.94931200 0.45572800 H 7.80360900 -3.85764700 0.24942300 H 7.09203500 -3.46217800 1.80356800 H 4.09051200 -2.59099900 1.48593400 H 1.87077500 -3.57965000 1.03667000 H 2.11781300 -2.27902600 -3.04599100 H 4.34160500 -1.30901000 -2.60937700 C -4.38358400 -3.65959700 -0.75042800 C -3.18565000 -3.45135300 -1.51433300 C -4.01525700 -3.75797900 0.64446300 C -1.94797900 -3.68666000 -0.64503400 C -2.58996900 -3.60735300 0.74370700 C -3.21704300 -2.57482300 -2.58048500 C -4.44565000 -1.90573600 -2.94192700 C -2.13198400 -1.60586600 -2.79392000 C -4.13717800 -0.56516600 -3.38653400 C -2.72011400 -0.38024700 -3.29184400 C -0.76225000 -2.62092500 -0.88584500 C -1.06686300 -1.55235700 -1.93008800 C -0.47489000 -1.71885800 0.31448200 C -0.57377300 -0.27516800 -1.50454700 C -0.21255900 -0.37679800 -0.12179100 C -2.06616000 -2.88740700 1.79544000 C -0.98385800 -1.91777100 1.57241200

C -2.93646100 -2.31582100 2.79679500 C -1.21015800 -0.79058200 2.45224600 C -2.40331300 -1.03596300 3.20530700 C -4.87026000 -3.24051700 1.63000900 C -4.31485900 -2.49974400 2.72618900 C -6.10116000 -2.57804200 1.24733600 C -5.20290600 -1.39649300 3.03947300 C -6.30960700 -1.44755900 2.12903300 C -5.59230100 -3.04457800 -1.11211400 C -6.45401300 -2.48259200 -0.09204400 C -5.61776600 -2.14525500 -2.22985200 C -7.02751000 -1.25266600 -0.59977000 C -6.50699200 -1.04215900 -1.91929600 C -1.04617500 0.95012700 -2.05650700 C -0.87720900 2.10985900 -1.25651000 C -0.31015800 0.74773700 0.74662700 C -0.51390100 2.00936600 0.12898700 C -0.82925000 0.52997000 2.09434600 C -1.52656500 1.58812300 2.73615700 C -3.25014000 0.02912300 3.62170700 C -2.72148100 1.34058200 3.48999800 C -4.70639600 -0.15801600 3.52782900 C -5.52283600 0.98117700 3.29431600 C -6.94861000 -0.25919800 1.67850700 C -6.62904400 0.93130900 2.38287100 C -7.32220900 -0.15769400 0.25902700 C -7.34701200 1.12633100 -0.34594900 C -6.27020400 0.26678600 -2.41837600 C -6.82806600 1.33558600 -1.66678800 C -5.04108700 0.51553000 -3.18767100 C -4.47034400 1.81581000 -3.15935000 C -2.16623700 0.89377000 -2.99314900 C -3.05163200 2.00291800 -3.06266000 C -5.11204500 2.90827700 -2.45503100 C -2.80910700 3.20850800 -2.29680000 C -4.08589200 3.78462000 -1.92848300 C -1.73939000 3.26215800 -1.41062800 C -1.14804300 3.10087800 0.83761600 C -1.90308000 3.89037700 -0.11481500 C -1.64824800 2.89215700 2.11774600 C -3.58711000 2.49418800 3.34326500 C -2.92012500 3.46775700 2.50311400 C -4.96090200 2.31768700 3.24465900 C -6.75061400 2.23717800 1.76171600

C -5.72882100 3.10646100 2.30515800 C -7.10320100 2.33301500 0.42234100 C -6.26705600 2.67222100 -1.72107700 C -6.44826900 3.30147700 -0.43080200 C -5.45790800 4.14254200 0.08719600 C -4.25000700 4.38722100 -0.67863700 C -3.13314300 4.44107000 0.24833600 C -3.65379900 4.22574600 1.58724500 C -5.09038000 4.04322400 1.48599900